Combination of adsorption/desorption and photocatalytic reduction processes for PFOA removal from water by using an aminated biosorbent and a UV/sulfite system.

Per- and polyfluoroalkyl substances (PFAS) are stable organic chemicals, which have been used globally since the 1940s and have caused PFAS contamination around the world. This study explores perfluorooctanoic acid (PFOA) enrichment and destruction by a combined method of sorption/desorption and photocatalytic reduction. A novel biosorbent (PG-PB) was developed from raw pine bark by grafting amine groups and quaternary ammonium groups onto the surface of bark particles. The results of PFOA adsorption at low concentration suggest that PG-PB has excellent removal efficiency (94.8%-99.1%, PG-PB dosage: 0.4 g/L) to PFOA in the concentration range of 10 µg/L to 2 mg/L. The PG-PB exhibited high adsorption efficiency regarding PFOA, being 456.0 mg/g at pH 3.3 and 258.0 mg/g at pH 7 with an initial concentration of 200 mg/L. The groundwater treatment reduced the total concentration of 28 PFAS from 18 000 ng/L to 9900 ng/L with 0.8 g/L of PG-PB. Desorption experiments examined 18 types of desorption solutions, and the results showed that 0.05% NaOH and a mixture of 0.05% NaOH + 20% methanol were efficient for PFOA desorption from the spent PG-PB. More than 70% (>70 mg/L in 50 mL) and 85% (>85 mg/L in 50 mL) of PFOA were recovered from the first and second desorption processes, respectively. Since high pH promotes PFOA degradation, the desorption eluents with NaOH were directly treated with a UV/sulfite system without further adjustment. The final PFOA degradation and defluorination efficiency in the desorption eluents with 0.05% NaOH + 20% methanol reached 100% and 83.1% after 24 h reaction. This study proved that the combination of adsorption/desorption and a UV/sulfite system for PFAS removal is a feasible solution for environmental remediation.

Ibuprofen degradation using a Co-doped carbon matrix derived from peat as a peroxymonosulphate activator.

The wider presence of pharmaceuticals and personal care products in nature is a major cause for concern in society. Among pharmaceuticals, the anti-inflammatory drug ibuprofen has commonly been found in aquatic and soil environments. We produced a Co-doped carbon matrix (Co-P 850) through the carbonization of Co2+ saturated peat and used it as a peroxymonosulphate activator to aid ibuprofen degradation. The properties of Co-P 850 were analysed using field emission scanning electron microscopy, energy filtered transmission electron microscopy and X-ray photoelectron spectroscopy. The characterization results showed that Co/Fe oxides were generated and tightly embedded into the carbon matrix after carbonization. The degradation results indicated that high temperature and slightly acidic to neutral conditions (pH = 5 to 7.5) promoted ibuprofen degradation efficiency in the Co-P 850/peroxymonosulphate system. Analysis showed that approx. 52% and 75% of the dissolved organic carbon was removed after 2 h and 5 h of reaction time, respectively. Furthermore, the existence of chloride and bicarbonate had adverse effects on the degradation of ibuprofen. Quenching experiments and electron paramagnetic resonance analysis confirmed that SO4·-, ·OH and O2·- radicals together contributed to the high ibuprofen degradation efficiency. In addition, we identified 13 degradation intermediate compounds and an ibuprofen degradation pathway by mass spectrometry analysis and quantum computing. Based on the results and methods presented in this study, we propose a novel way for the synthesis of a Co-doped catalyst from spent NaOH-treated peat and the efficient catalytic degradation of ibuprofen from contaminated water.

Production of aminated peat from branched polyethylenimine and glycidyltrimethylammonium chloride for sulphate removal from mining water.

A novel bio-based anion exchanger was developed to remove sulphate from synthetic solutions and mine water. Different modification parameters such as chemical dosage and reaction time were tested when using a unique combination of branched polyethylenimine (PEI) and glycidyltrimethylammonium chloride (GTMAC) to produce an aminated biosorbent (termed PG-Peat). The novel and environment-friendly modification method was shown by FTIR and XPS analyses to be able to introduce quaternary ammonium and N-H groups into PG-Peat. The optimal modification conditions (PEI: 0.26 mmol/g, GTMAC: 0.0447 mol/g, reaction time: 18 h) resulted in the maximum sulphate uptake capacity (189.5 ±â€¯2.7 mg/g) with a partition coefficient value of 0.02 mg/g/µM under acidic conditions. At low pH, amine groups on the peat surface became cationized, thereby resulting in a higher sulphate removal capacity. Batch sorption tests using PG-Peat exhibited rapid sulphate sorption after only five minutes of contact. The sulphate uptake by PG-Peat was unaffected by the presence of varying chloride concentrations, while slightly lower uptake capacity was observed when different concentrations of nitrate were present. The biosorbent showed high recyclability, which was revealed in regeneration studies. Tests were performed involving real mine water, where PG-Peat showed its potential to be a highly efficient biosorbent for sulphate removal at low pH values, indicating its suitability for treating acidic mine waters.

Removal of metals from mine drainage waters by in situ mineral sorbent-based pilot filter systems.

Discharge of metal-containing wastewater streams into the environment is an environmental concern because these pollutants do not degrade and tend to bioaccumulate. A number of laboratory-based investigations on the effectiveness of a wide range of filter materials for metal removal from diluted wastewater streams have been reported. However, only a few pilot or full-scale investigations have been conducted. Therefore, this study investigated the metal retention capabilities of mineral-based filter materials (commercially available mineral product (5-15 mm), recycled mineral material (2-4 mm) and slag by-product (2-4 and 4-16 mm)) when used in pilot-scale filter systems under continuous operation in a closed mining area in North Ostrobothnia, Finland, between June and October 2017. The influence of material particle size on system function and on metal retention efficiency was also evaluated. The results revealed that system performance was dependent on material composition and particle size (smaller particle size being more effective). The highest metal removal efficiencies (Zn, Ni, Cd, Cu and Pb) and largest amount of water treated (per volume of material applied) were achieved by an aluminium oxide-based recycled mineral material (2-4 mm). While smaller-grained materials performed better in terms of removal efficiency, the removal rates achieved by coarser-grained, commercially available mineral product (5-15 mm) were comparable to those achieved by small-grained slag (2-4 mm). Full-scale systems using the recycled mineral product (2-4 mm) would have an approximately two-fold longer material replacement time than systems using the slag (2-4 mm). Replacement time for the larger-grained materials tested could not be determined, due to problems with freezing. Overall, the recycled mineral material tested can be recommended for full-scale tests, especially when high zinc removal rates are required.

Enhancing peat metal sorption and settling characteristics.

Peat is an excellent material for metal sorption since it naturally contains different kinds of functional groups that can sorb metal cations from water. The main objective of this work was to test low-cost treatment (acid and alkali) methods for natural peat, which would improve the settling properties of peat particles while maintaining its metal removal efficiency. Particularly, the poor settling properties of peat hinder its practical application. The study revealed that NaOH-treated peat (0.1M) had excellent settling properties and could be applied in wastewater applications having mixing and settling systems without a settling aid. The superior leaching of humic and fulvic acids in alkaline treatment caused a change in morphology, making it a harder and sticky material. Moreover, the NaOH-treated (0.1M) peat was proven to be the most efficient material for nickel removal followed by the HCl-treated (0.2M) peat, citric acid-treated (0.16M) peat and water-treated peat. A higher temperature and longer time slightly increased the Ni removal efficiency with NaOH-treated peat material. The settling of HCl-treated peat was studied further using polyacrylamide flocculants (cationic, neutral, anionic). Cationic flocculants performed best and the cationic charge density also had an effect on the flocculation performance of peat particles. This study provides further evidence that peat can be applied in the treatment of metal-containing wastewaters.

Evaluating the influence of pH adjustment on chemical purification efficiency and the suitability of industrial by-products as alkaline agents.

Metal salts of iron are currently used in several treatment facilities purifying peat extraction runoff water. Although chemical purification is considered best available technology for the treatment of this natural humic water, fluctuations in purification efficiency occur with low pH (3-4) and high metal concentration found in treated waters. The need for pH neutralisation increases the costs and overall environmental impacts related to chemical purification. The use of industrial by-products can decrease costs while supporting the sustainable use of natural resources and the principle of a circular economy. This study investigated the suitability of a range of calcium-based alkaline products (including by-products of the paper, cement and mineral industries) for neutralisation of chemically treated runoff water. The influence of the time of pH adjustment relative to time of coagulant addition (before coagulant, after but within coagulation, during flocculation and after sedimentation) on purification efficiency was evaluated. The hypotheses that the physical form of the coagulant was a relevant factor affecting purification was also assessed. The best performing pH-adjusting products were cement kiln dust (CaO and SiO2) and Mahtikalkki (Ca(OH)2, CaCO3 and CaO), by-products of the cement and paper industry, respectively. Time of pH adjustment in relation to time of coagulation addition had a significant influence on purification efficiency, especially when solid coagulant was used. Adjustment of pH at 30 s before coagulant dosing resulted in a negative effect on treatment results. Based on results obtained, suitable points of pH adjustment are during the flocculation stage or at the outlet of sedimentation, particularly if solid coagulants are used.

Removal of metals from industrial wastewater and urban runoff by mineral and bio-based sorbents.

The study was performed to evaluate chemically modified biosorbents, hydrochloric acid treated peat (HCl-P) and citric acid treated sawdust (Citric acid-SD) for their metal removal capacity from dilute industrial wastewater and urban runoff and compare their efficiency with that of commercially available mineral sorbents (AQM PalPower M10 and AQM PalPower T5M5 magnetite). Batch and column experiments were conducted using real water samples to assess the sorbents' metal sorption capacity. AQM PalPower M10 (consisting mainly of magnesium, iron and silicon oxides) exhibited excellent Zn removal from both industrial wastewater and spiked runoff water samples even at low dosages (0.1 g/L and 0.05 g/L, respectively). The high degree of Zn removal was associated with the release of hydroxyl ions from the sorbent and subsequent precipitation of zinc hydroxide. The biosorbents removed Ni and Cr better than AQM PalPower M10 from industrial wastewater and performed well in removing Cr and Cu from spiked runoff water, although at higher dosages (0.3-0.75 g/L). The main mechanism of sorption by biosorbents was ion exchange. The sorbents required a short contact time to reach equilibrium (15-30 min) in both tested water samples. AQM PalPower T5M5 magnetite was the worst performing sorbent, leaching Zn into both industrial and runoff water and Ni into runoff water. Column tests revealed that both HCl-P and AQM PalPower M10 were able to remove metals, although some leaching was witnessed, especially As from AQM PalPower M10. The low hydraulic conductivity observed for HCl-P may restrict the possibilities of using such small particle size peat material in a filter-type passive system.

Iron-loaded Sphagnum moss extract residue for phosphate removal.

Sphagnum moss extract residue (SMER), obtained after pressurized hot water extraction, was modified with Fe(III) and investigated for phosphate sorption. Although moss extract contains value-added compounds, SMER is considered to be waste until suitable uses can be developed. The effect of modification conditions were investigated, i.e. different initial Fe(III) concentrations (0.024, 0.048 and 0.072 mol/L Fe3+) and modification pH values (5, 7 and 9). A modification pH of 5 and the highest initial Fe(III) concentration (0.072 mol/L Fe3+) resulted in the highest phosphate removal efficiency, and thus was selected for further study. The removal efficiency was found to decrease with increasing pH in the range of 3-9. Maximum removal efficiency (82%) for phosphate sorption was observed at pH 3 after 24 h contact time (dosage 2 g/L, initial concentration 15 mg P/L). With increased contact time, the phosphate removal efficiency improved and reached equilibrium within 48 h. The Elovich model was found to provide the best fit to the kinetic data. A capacity of 9-13 mg P/g was obtained with a 24-h contact time at pH 4. A good fit was achieved with the Redlich-Peterson equation. FTIR analysis confirmed that carboxylic acid groups were involved in the modification process. X-ray diffraction analyses showed that amorphous two-line ferrihydrite was precipitated onto SMER, which was supported by X-ray photoelectron spectroscopy analyses.

Removal of vanadium from industrial wastewater using iron sorbents in batch and continuous flow pilot systems.

This study investigated the removal of vanadium from real industrial wastewater by using six iron materials: commercial iron sorbent (CFH-12), commercial mineral sorbent (AQM), blast furnace sludge (BFS), steel converter sludge (SCS), ferrochrome slag (FeCr) and slag from a steel foundry (OKTO). Batch tests revealed that CFH-12 (ferric oxyhydroxide) removed vanadium most efficiently, which was explained by its high iron content and the amorphous form of the iron, and that the sorption followed the Langmuir isotherm. With a dosage of 10 g/l and an initial vanadium concentration of 58.2 mg/l, 91-94% removal rates for vanadium were achieved in the studied pH range (3-9). Other sorbents showed significantly lower efficiency than CFH-12, with the exception of BFS at acidic pH (93%). Based on the batch test results, CFH-12 was selected for a pilot study made on site. The pilot study demonstrated the feasibility of CFH-12 to remove vanadium at high temperature (80 °C) from concentrated industrial wastewater with fluctuating water quality (vanadium concentration varied from 51 to 83 mg/l, pH about 9 (at 25 °C)). Leaching of impurities (mainly S, Ca, Mg and K) into the effluent occurred during the first day, but subsequently good quality effluent was produced (e.g. <0.1 mg/l V). During the pilot study, the amorphous iron material of CFH-12 was crystallized into a hematite-like phase (Fe1.67 H0.99 O3), and goethite (FeO(OH)) with a higher average pore diameter, probably due to the hot process conditions to which CFH-12 was exposed for over five days.

Properties of vanadium-loaded iron sorbent after alkali regeneration.

The aim of this research was to investigate the regeneration and reuse of a commercial granular iron sorbent (mainly goethite) when used in vanadium removal. A regeneration rate of 3 M NaOH was the highest (85%) achieved, followed by 2 M NaOH (79%) and 1 M NaOH (68%). The breakthrough curves show that the regenerated material can be reused. The BET (Brunauer-Emmett-Teller) surface area increased by 35-38% and the total pore volume increased by 123-130% as a consequence of NaOH treatment. The results indicated that sodium hydroxide could be used for the regeneration of iron sorbent although the regeneration was incomplete. This may be explained by the fact that vanadium diffusion into pores is a significant sorption mechanism in addition to complex formation with surface functional groups. As a consequence, vanadium desorbability from pores is not as effective as the regeneration of surface sites. X-ray photoelectron spectroscopy analyses confirmed a very low vanadium content on the surface of the NaOH-treated iron sorbent.

Coagulation of humic waters for diffused pollution control and the influence of coagulant type on DOC fractions removed.

This study examined the suitability of organic coagulants for treatment of typically humic peat extraction runoff water by comparing their performance with that of ferric sulphate (FS). The influence of coagulant type on dissolved organic carbon (DOC) fractions removed was analysed in detail using LC-OCD-OND (size exclusion liquid chromatography coupled with organic carbon and organic nitrogen detection) fractionation techniques. In general, lower coagulant dosage was needed under acidic (pH 4.5) than neutral (pH 6.5) conditions. Chitosan (Chit) and poly (diallyldimethyl) ammonium chloride (pDMAC) required significantly lower dosage (40-55%) than FS for acceptable purification, while a tannin-based coagulant (Tan2) required substantially higher dosage (55-75%) independent of water pH. FS demonstrated the best removal of DOC (<81%) and phosphorus (<93%) followed by pDMAC, while Chit and Tan2 achieved the highest removal of suspended solids (SS) (<58%), with flocs formed by Tan2 presenting the best settling properties. Higher molecular weight (MW) DOC fractions were more efficiently removed by all coagulants, with FS being the most efficient (biopolymers 69% and humic substances 91%), followed by Tan2. FS also displayed satisfactory removal of lower MW fractions (building blocks ∼46% and low MW neutrals 62%). Overall, FS was the best performing coagulant. Nevertheless, the organic polymers demonstrated satisfactory overall performance, achieving purification rates mostly inside the requirements set by Finnish environmental authorities.

Characteristics and settling behaviour of particles from blast furnace flue gas washing.

A lot of particles from iron-making are removed with blast furnace off-gas and routed to the gas cleaning system. As water is used for cleaning the gas, the produced wash water contains a large amount of particles such as valuable Fe and C. However, the presence of zinc prevents recycling. In addition, the high amount of calcium results in uncontrolled scaling. Therefore, the properties of the wash water from scrubber and sludge, from the Finnish metal industry (SSAB Raahe), were evaluated in this study. Size fractionation of wash water revealed that Fe, Zn, Al, Mn, V, Cr and Cd appeared mainly in the larger fractions (>1.2 µm) and Na, Mg, Si, Ni, K, Cu and As appeared mainly in the smaller fractions (<1.2 µm) or in dissolved form. Calcium was found both in the larger fractions and dissolved (∼60 mg/L). Most of the particles in wash water were included in the 1.2-10 µm particle size and were settled effectively. However, a clear benefit was observed when using a chemical to enhance particle settling. In comparison to 2.5 h of settling without chemical, the turbidity was further decreased by about 94%, iron 85% and zinc 50%. Coagulation-flocculation experiments indicated that both low and high molecular weight cationic polymers could provide excellent purification results in terms of turbidity. Calcium should be removed by other methods. The particles in sludge were mostly in the 2-4 µm or 10-20 µm fractions. Further sludge settling resulted in high solids removal.

Chemical treatment response to variations in non-point pollution water quality: results of a factorial design experiment.

Chemical treatment of non-point derived pollution often suffers from undesirable oscillations in purification efficiency due to variations in runoff water quality. This study examined the response of the chemical purification process to variations in water quality using a 2(k) factorial design for runoff water rich in humic substances. The four k factors evaluated and the levels applied were: organic matter as dissolved organic carbon (DOC) (20-70 mg/L), suspended solids (SS) (10-60 mg/L), initial water pH (4.5-7), and applied coagulant dosage (ferric sulphate) (35-100 mg/L). Indicators of purification efficiency were residual concentration of DOC, SS and total phosphorus (tot-P). Analysis of variance and factor effect calculations showed that the initial DOC concentration in raw water samples and its interactions with the coagulant dosage applied exerted the most significant influence on the chemical purification process, substantially affecting the residual concentration of DOC, SS and tot-P. The variations applied to the factors SS and pH only slightly affected purification efficiency. The results can be used in the design of purification systems with high organic matter load variation, e.g. peat extraction runoff.

Removal of nitrate by modified pine sawdust: effects of temperature and co-existing anions.

The effect of temperature, sulphate and phosphate, and the initial nitrate concentration on nitrate removal was studied with synthetic solutions. Chemically modified pine sawdust (Pinus sylvestris) anion exchange resin (MPSD) was used in the sorption studies. The resin was synthesized by reacting pine sawdust with epichlorohydrin, ethylenediamine and triethylamine in the presence of N,N-dimethylformamide. Nitrate removal was successful at 5-70 °C. Higher temperatures caused nitrate removal to decrease moderately, but sorption capacities of 22.2-32.8 mg/g for NO3-N were achieved. The removal of nitrate in the presence of sulphate or phosphate was studied at concentrations of 30 mg N/l, 10-500 mg S/l and 1-50 mg P/l. A significant decrease in nitrate reduction was observed at sulphate and phosphate concentrations of 100 mg S/l and 50 mg P/l, respectively. The effect of initial nitrate concentration was studied in column. Nitrate sorption was clearly dependent on the initial concentration. Desorption of nitrate in column was completed using about 80 bed volumes of 0.1 M NaCl solution. The sorption data were fitted to the Langmuir, Freundlich and Redlich-Peterson adsorption models. The Redlich-Peterson and Langmuir models gave the best fit, which suggests monolayer sorption. Thermodynamic studies revealed that the sorption of nitrate was spontaneous and exothermic in nature. The results imply that modified pine sawdust could be a feasible alternative in the treatment of real industrial wastewaters.

Preparation of cationized pine sawdust for nitrate removal: Optimization of reaction conditions.

Anion exchange materials were prepared from pine sawdust (Pinus sylvestris, PSD) through cationizing treatment with N-(3-chloro-2-hydroxypropyl) trimethyl ammonium chloride (CHMAC) in the presence of NaOH. Response surface methodology (RSM) was used to find the optimal reaction conditions. Three factors were chosen: reaction temperature (26-94 °C), reaction time (0.32-3.7 h) and NaOH/CHMAC molar ratio (0.19-2.2). Product yield (%) was used as a response. A quadratic model was fitted to the experimental data. The optimal conditions were: a reaction temperature of 57 °C, a reaction time of 1.8 h and a NaOH/CHMAC molar ratio of 1.32. A maximum nitrogen content of 2.6% was obtained at 60 °C, 3.7 h and a molar ratio of 1.2. The molar ratio had the greatest impact on the response. Regression analysis revealed that over 95% of the variance can be explained by the model. A maximum nitrate sorption capacity of 15.3 ± 1.4 mg N/g was achieved. The effect of CHMAC dose was also studied (a NaOH/CHMAC molar ratio of 1.2): 0.064 mol/g PSD was found to be near the optimum. Nitrate-contaminated groundwater (27.5 mg/l NO3) was treated with CPSD. Doses of 3-6 g/l resulted in 59-71% nitrate reduction.

Vanadium removal from mining ditch water using commercial iron products and ferric groundwater treatment residual-based materials.

Removal of vanadium from liquid waste streams protects the environment from toxic vanadium species and promotes the recovery of the valuable metal. In this study, real mining ditch water was sampled from a closed vanadium mine (V-Fe-Ti oxide deposit, Finland) and used in sorption experiments at prevailing vanadium concentration (4.66-6.85 mg/L) and pH conditions (7.02-7.83). The high concentration of vanadium in the water represents a potential health concern according to the initial risk assessment carried out in this study. Vanadium was efficiently removed using four different iron sorbents: ferric oxyhydroxide with some goethite (CFH-12), poorly crystallized akaganéite (GEH 101), ferric groundwater treatment residual (GWTR), and GWTR-modified peat (GWTR-Peat). Higher dosage (6 g/L with 24 h contact time) and longer contact time (72 h using 1 g/L dosage) resulted in removal efficiencies of higher than 85%. Kinetic data were well represented by the Elovich model while intra-particle diffusion and Boyd models suggested that the sorption process in a real water matrix was significantly controlled by both film diffusion and intra-particle diffusion. Column studies with CFH-12, GEH 101, and GWTR-Peat showed that the breakthrough started earlier with the mining ditch water compared to a synthetic vanadium solution (investigated only with CFH-12), whereas GEH 101 proved to have the best performance in column mode. The Thomas and Yoon-Nelson column models were found to agree with the experimental data fairly well with the 50% breakthrough time being close to the experimental value for all the studied sorbents.

Bioregeneration of sulfate-laden anion exchange resin.

Ion exchange technology removes ionic compounds from waters effectively but treatment of the spent regenerant is expensive. The bioregeneration of sulfate-laden strong base anion exchange resin was successfully tested using both pure and mixed sulfate-reducing bacterial cultures. The resin was first used for removal of sulfate from neutral (pH 6.7 ± 0.5) synthetic sodium sulfate solutions, after which the spent resin was regenerated by incubating with a viable sulfate-reducing bacterial culture in batch and column modes. In the batch bioregeneration tests, the achieved bioregeneration was 36-95% of the original capacity of the fresh resin (112 mg SO42-/g) and it increased with regeneration time (1-14 days). The capacity achieved in the column tests during 24 hours of bioregeneration was 107 mg SO42-/g after the first regeneration cycle. During the bioregeneration, sulfate was mainly reduced by the sulfate-reducing bacteria (approx. 60%), but part of it was only detached from the resins (approx. 30%). The resin-attached sulfate was most likely replaced with ions present in the liquid sulfate-reducing bacterial culture (e.g., HCO3-, HS-, and Cl-). During the subsequent exhaustion cycles with the bioregenerated resin, the pH of the treated sodium sulfate solution increased from the original 6.7 ± 0.5 to around 9. The study showed that biological sulfate reduction could be used for sulfate removal in combination with ion exchange, and that the exhausted ion exchange resins could be regenerated using a liquid sulfate-reducing bacterial culture without producing any brine.

The Role of Zeolite Structure in Its ß-cyclodextrin Modification and Tetracycline Adsorption from Aqueous Solution: Characteristics and Sorption Mechanism.

Modification of zeolites with organic compounds is of increasing interest due to their significant potential in removing emerging pollutants from water. In this work, zeolites from fly ash with three different structure types, NaX (faujasite), NaA (Linde A) and NaP1 (gismondine), were modified with ß-cyclodextrin (ß-CD), and their adsorption efficacy towards tetracycline (TC) antibiotic in aqueous solutions have been studied. To assess the effect of modification on the zeolites, they were subjected to chemical, mineralogical and surface analyses using X-ray diffraction (XRD), thermogravimetry (TG), scanning electron microscope (SEM), N2 adsorption/desorption isotherm, Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The maximum adsorption capacity for NaX-CD, NaA-CD and NaP1-CD was around 48, 60, and 38 mg/g, respectively. The fastest adsorption rate was observed for NaP1-CD, which achieved adsorption equilibria after 200 min, while for NaX-CD and NaA-CD it was established after around 24 h. The kinetic data were best described by the Elovich model, followed by pseudo-second order, while the Sips and Redlich-Peterson models were the most suitable to describe the adsorption isotherms. Based on the adsorption data as well as FTIR and XPS results, TC adsorption efficacy is strongly related to the amount of CD attached to the mineral, and hydrogen bonding formation probably plays the major role between CDs and adsorbate.

Suitability of natural and chemically modified peat as a sorbent material for mining water purification in small-scale pilot systems.

In this study, the suitability of natural peat (Nat-Peat) and HCl-modified peat (M-Peat) as a sorbent for purification of mining water was evaluated in two different small-scale pilot systems: a continuous stirred tank reactor (CSTR) and a horizontal flow filter (HFF). The effect of process parameters (peat type, peat dose, mixing time, mixing intensity) on metal (metalloid) removal in the CSTR system was also investigated. In the CSRT, Nat-Peat achieved higher removal of Ni (<80%) and As (∼61%) than M-Peat (72% and 26% for Ni and As, respectively). In the HFF, Nat-Peat achieved slightly lower maximum removal of Ni (<96%) than M-Peat (<98%) and higher removal of As and Sb (<87% and 8%) than M-Peat (<35% and 7%). Thus, chemical modification (HCl) of peat did not improve its affinity for metal and metalloids. Among the process parameters studied, peat dose exerted the strongest effect on residual concentrations of Ni, As and Sb. Higher removal of Ni and As was achieved in treatment combinations involving high peat dose (2 g/L), mixing time (60 min) and mixing intensity (300 rpm), but the effect of increasing level of these factors was not linear. This study showed that peat can be a viable sorbent material in CSTR systems (followed by sedimentation) if sorbent particle removal can be improved. Use of peat in HFF systems is not viable, due to its inability to cope with large water volumes.

Vertically co-distributed vanadium and microplastics drive distinct microbial community composition and assembly in soil.

Vanadium (V) and microplastics in soils draw increasing attention considering their significant threats to ecosystems. However, little is known about the vertical co-distribution of V and microplastics in soil profile and their combined effects on microbial community dynamics and assembly. This study investigated the spatial distribution of V and microplastics in the soils at a V smelting site and the associated microbial community characteristics along the vertical gradient. Both V and microplastics were found in the 50 cm soil profile with average concentrations of 203.5 ± 314.4 mg/kg and 165.1 ± 124.8 item/kg, respectively. Topsoil (0-20 cm) and subsoil (20-50 cm) displayed distinct microbial community compositions. Metal-tolerant (e.g., Spirochaeta, Rubellimicrobium) and organic-degrading (e.g., Bradyrhizobium, Pseudolabrys) taxa as biomarkers were more abundant in the topsoil layer. V and microplastics directly affected the microbial structure in the topsoil and had indirect influences in the subsoil, with direct impacts from organic matter. In topsoil, deterministic processes were more prevalent for community assembly, whereas stochastic processes governed the subsoil. The interspecific relationship was closer in topsoil with greater network complexity and higher modularity. These findings promote the understanding of distinct heterogeneity of microbial communities jointly driven by V and microplastics in soil environment.